Periodic structured organic films

ABSTRACT

An ordered structured organic film comprising a plurality of segments and a plurality of linkers arranged as a covalent organic framework, wherein the structured organic film may be a multi-segment thick structured organic film.

This nonprovisional application claims the benefit of U.S. patentapplication Ser. Nos. 12/716,524; 12/716,449; 12/716,706; 12/716,324;12/716,686; and 12/716,571, entitled “Structured Organic Films,”“Structured Organic Films Having an Added Functionality,” “Mixed SolventProcess for Preparing Structured Organic Films,” “Composite StructuredOrganic Films,” “Process For Preparing Structured Organic Films (SOFs)Via a Pre-SOF,” “Electronic Devices Comprising Structured OrganicFilms,” each of which claims the benefit of U.S. Provisional ApplicationNo. 61/157,411, entitled “Structured Organic Films” filed Mar. 4, 2009,the disclosures of which are totally incorporated herein by reference intheir entireties.

CROSS-REFERENCE TO RELATED APPLICATIONS

Commonly assigned U.S. patent application Ser. Nos. 12/716,524;12/716,449; 12/716,706; 12/716,324; 12/716,686; and 12/716,571, entitled“Structured Organic Films,” “Structured Organic Films Having an AddedFunctionality,” “Mixed Solvent Process for Preparing Structured OrganicFilms,” “Composite Structured Organic Films,” “Process For PreparingStructured Organic Films (SOFs) Via a Pre-SOF,” “Electronic DevicesComprising Structured Organic Films,” respectively, the disclosures ofwhich are totally incorporated herein by reference in their entireties,describe structured organic films, methods for preparing structuredorganic films and applications of structured organic films.

BACKGROUND OF THE INVENTION

Materials whose chemical structures are comprised of molecules linked bycovalent bonds into extended structures may be placed into two classes:(1) polymers and cross-linked polymers, and (2) covalent organicframeworks (also known as covalently linked organic networks).

The first class, polymers and cross-linked polymers, is typicallyembodied by polymerization of molecular monomers to form long linearchains of covalently-bonded molecules. Polymer chemistry processes canallow for polymerized chains to, in turn, or concomitantly, become‘cross-linked.’ The nature of polymer chemistry offers poor control overthe molecular-level structure of the formed material, i.e. theorganization of polymer chains and the patterning of molecular monomersbetween chains is mostly random. Nearly all polymers are amorphous, savefor some linear polymers that efficiently pack as ordered rods. Somepolymer materials, notably block co-polymers, can possess regions oforder within their bulk. In the two preceding cases the patterning ofpolymer chains is not by design, any ordering at the molecular-level isa consequence of the natural intermolecular packing tendencies.

The second class, covalent organic frameworks (COFs), differ from thefirst class (polymers/cross-linked polymers) in that COFs are intendedto be highly patterned. In COF chemistry molecular components are calledmolecular building blocks rather than monomers. During COF synthesismolecular building blocks react to form two- or three-dimensionalnetworks. Consequently, molecular building blocks are patternedthroughout COF materials and molecular building blocks are linked toeach other through strong covalent bonds.

COFs developed thus far are typically powders with high porosity and arematerials with exceptionally low density. COFs can store near-recordamounts of argon and nitrogen. While these conventional COFs are useful,there is a need, addressed by embodiments of the present invention, fornew materials that offer advantages over conventional COFs in terms ofenhanced characteristics.

SUMMARY OF THE DISCLOSURE

There is provided in embodiments an ordered (periodic) structuredorganic film comprising a plurality of segments and a plurality oflinkers arranged as a covalent organic framework, wherein at amacroscopic level the covalent organic framework is a film.

BRIEF DESCRIPTION OF THE DRAWINGS

Other aspects of the present disclosure will become apparent as thefollowing description proceeds and upon reference to the followingfigures which represent illustrative embodiments:

FIG. 1 is a graphic representation that compares the Fourier transforminfrared spectral of the products of control experiments mixtures,wherein onlyN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine isadded to the liquid reaction mixture (top), wherein onlybenzene-1,4-dimethanol is added to the liquid reaction mixture (middle),and wherein the necessary components needed to form a patterned Type 2SOF are included into the liquid reaction mixture (bottom).

FIG. 2 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprisingN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine segments, p-xylylsegments, and ether linkers.

FIG. 3 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprisingN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine segments, n-hexylsegments, and ether linkers.

FIG. 4 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprisingN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine segments,4,4′-(cyclohexane-1,1-diyl)diphenyl, and ether linkers.

FIG. 5 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprising of triphenylamine segmentsand ether linkers.

FIG. 6 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprising triphenylamine segments,benzene segments, and imine linkers.

FIG. 7. is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprising triphenylamine segments, andimine linkers.

FIG. 8 is a graphic representation of two-dimensional X-ray scatteringdata for the SOFs produced in Examples 26 and 54.

DETAILED DESCRIPTION

“Structured organic film” (SOF) is a new term introduced by the presentdisclosure to refer to a COF that is a film at a macroscopic level. Theterm “SOF” refers to a covalent organic framework (COF) that is a filmat a macroscopic level. The phrase “macroscopic level” refers, forexample, to the naked eye view of the present SOFs. Although COFs are anetwork at the “microscopic level” or “molecular level” (requiring useof powerful magnifying equipment or as assessed using scatteringmethods), the present SOF is fundamentally different at the “macroscopiclevel” because the film is for instance orders of magnitude larger incoverage than a microscopic level COF network. SOFs described hereinhave macroscopic morphologies much different than typical COFspreviously synthesized. COFs previously synthesized were typicallyobtained as polycrystalline or particulate powders wherein the powder isa collection of at least thousands of particles (crystals) where eachparticle (crystal) can have dimensions ranging from nanometers tomillimeters. The shape of the particles can range from plates, spheres,cubes, blocks, prisms, etc. The composition of each particle (crystal)is the same throughout the entire particle while at the edges, orsurfaces of the particle, is where the segments of the covalently-linkedframework terminate. The SOFs described herein are not collections ofparticles. Instead, the SOFs of the present disclosure are at themacroscopic level substantially defect-free SOFs or defect-free SOFshaving continuous covalent organic frameworks that can extend overlarger length scales such as for instance much greater than a millimeterto lengths such as a meter and, in theory, as much as hundreds ofmeters. It will also be appreciated that SOFs tend to have large aspectratios where typically two dimensions of a SOF will be much larger thanthe third. SOFs have markedly fewer macroscopic edges and disconnectedexternal surfaces than a collection of COF particles.

In embodiments, a “substantially defect-free SOF” or “defect-free SOF”may be formed from a reaction mixture deposited on the surface of anunderlying substrate. The term “substantially defect-free SOF” refers,for example, to an SOF that may or may not be removed from theunderlying substrate on which it was formed and contains substantiallyno pinholes, pores or gaps greater than the distance between the coresof two adjacent segments per square cm; such as, for example, less than10 pinholes, pores or gaps greater than about 250 nanometers in diameterper cm², or less than 5 pinholes, pores or gaps greater than about 100nanometers in diameter per cm². The term “defect-free SOF” refers, forexample, to an SOF that may or may not be removed from the underlyingsubstrate on which it was formed and contains no pinholes, pores or gapsgreater than the distance between the cores of two adjacent segments permicron², such as no pinholes, pores or gaps greater than about 100Angstroms in diameter per micron², or no pinholes, pores or gaps greaterthan about 50 Angstroms in diameter per micron², or no pinholes, poresor gaps greater than about 20 Angstroms in diameter per micron².

In embodiments, the SOF comprises at least one atom of an element thatis not carbon, such at least one atom selected from the group consistingof hydrogen, oxygen, nitrogen, silicon, phosphorous, selenium, fluorine,boron, and sulfur. In further embodiments, the SOF is a boroxine-,borazine-, borosilicate-, and boronate ester-free SOF.

Molecular Building Block

The SOFs of the present disclosure comprise molecular building blockshaving a segment (S) and functional groups (Fg). Molecular buildingblocks require at least two functional groups (x≧2) and may comprise asingle type or two or more types of functional groups. Functional groupsare the reactive chemical moieties of molecular building blocks thatparticipate in a chemical reaction to link together segments during theSOF forming process. A segment is the portion of the molecular buildingblock that supports functional groups and comprises all atoms that arenot associated with functional groups. Further, the composition of amolecular building block segment remains unchanged after SOF formation.

Functional Group

Functional groups are the reactive chemical moieties of molecularbuilding blocks that participate in a chemical reaction to link togethersegments during the SOF forming process. Functional groups may becomposed of a single atom, or functional groups may be composed of morethan one atom. The atomic compositions of functional groups are thosecompositions normally associated with reactive moieties in chemicalcompounds. Non-limiting examples of functional groups include halogens,alcohols, ethers, ketones, carboxylic acids, esters, carbonates, amines,amides, imines, ureas, aldehydes, isocyanates, tosylates, alkenes,alkynes and the like.

Molecular building blocks contain a plurality of chemical moieties, butonly a subset of these chemical moieties are intended to be functionalgroups during the SOF forming process. Whether or not a chemical moietyis considered a functional group depends on the reaction conditionsselected for the SOF forming process. Functional groups (Fg) denote achemical moiety that is a reactive moiety, that is, a functional groupduring the SOF forming process.

In the SOF fanning process the composition of a functional group will bealtered through the loss of atoms, the gain of atoms, or both the lossand the gain of atoms; or, the functional group may be lost altogether.In the SOF, atoms previously associated with functional groups becomeassociated with linker groups, which are the chemical moieties that jointogether segments. Functional groups have characteristic chemistries andthose of ordinary skill in the art can generally recognize in thepresent molecular building blocks the atom(s) that constitute functionalgroup(s). It should be noted that an atom or grouping of atoms that areidentified as part of the molecular building block functional group maybe preserved in the linker group of the SOF. Linker groups are describedbelow.

Segment

A segment is the portion of the molecular building block that supportsfunctional groups and comprises all atoms that are not associated withfunctional groups. Further, the composition of a molecular buildingblock segment remains unchanged after SOF formation. In embodiments, theSOF may contain a first segment having a structure the same as ordifferent from a second segment. In other embodiments, the structures ofthe first and/or second segments may be the same as or different from athird segment, forth segment, fifth segment, etc. A segment is also theportion of the molecular building block that can provide an inclinedproperty. Inclined properties are described later in the embodiments.

In specific embodiments, the segment of the SOF comprises at least oneatom of an element that is not carbon, such at least one atom selectedfrom the group consisting of hydrogen, oxygen, nitrogen, silicon,phosphorous, selenium, fluorine, boron, and sulfur.

A description of various exemplary molecular building blocks, linkers,SOF types, strategies to synthesize a specific SOF type with exemplarychemical structures, building blocks whose symmetrical elements areoutlined, and classes of exemplary molecular entities and examples ofmembers of each class that may serve as molecular building blocks forSOFs are detailed in U.S. patent application Ser. Nos. 12/716,524;12/716,449; 12/716,706; 12/716,324; 12/716,686; and 12/716,571, entitled“Structured Organic Films,” “Structured Organic Films Having an AddedFunctionality,” “Mixed Solvent Process for Preparing Structured OrganicFilms,” “Composite Structured. Organic Films,” “Process For PreparingStructured Organic Films (SOFs) Via a Pre-SOF,” “Electronic DevicesComprising Structured Organic Films,” the disclosures of which aretotally incorporated herein by reference in their entireties.

Metrical Parameters of SOFs

SOFs have any suitable aspect ratio. In embodiments, SOFs have aspectratios for instance greater than about 30:1 or greater than about 50:1,or greater than about 70:1, or greater than about 100:1, such as about1000:1. The aspect ratio of a SOF is defined as the ratio of its averagewidth or diameter (that is, the dimension next largest to its thickness)to its average thickness (that is, its shortest dimension). The term‘aspect ratio,’ as used here, is not bound by theory. The longestdimension of a SOF is its length and it is not considered in thecalculation of SOF aspect ratio.

Generally, SOFs have widths and lengths, or diameters greater than about500 micrometers, such as about 10 mm, or 30 mm. The SOFs have thefollowing illustrative thicknesses: about 10 Angstroms to about 250Angstroms, such as about 20 Angstroms to about 200 Angstroms, for amono-segment thick layer and about 20 nm to about 5 mm, about 50 nm toabout 10 mm for a multi-segment thick layer.

SOF dimensions may be measured using a variety of tools and methods. Fora dimension about 1 micrometer or less, scanning electron microscopy isthe preferred method. For a dimension about 1 micrometer or greater, amicrometer (or ruler) is the preferred method.

Multilayer SOFs

A SOF may comprise a single layer or a plurality of layers (that is,two, three or more layers). SOFs that are comprised of a plurality oflayers may be physically joined (e.g., dipole and hydrogen bond) orchemically joined. Physically attached layers are characterized byweaker interlayer interactions or adhesion; therefore physicallyattached layers may be susceptible to delamination from each other.Chemically attached layers are expected to have chemical bonds (e.g.,covalent or ionic bonds) or have numerous physical or intermolecular(supramolecular) entanglements that strongly link adjacent layers.

Therefore, delamination of chemically attached layers is much moredifficult. Chemical attachments between layers may be detected usingspectroscopic methods such as focusing infrared or Raman spectroscopy,or with other methods having spatial resolution that can detect chemicalspecies precisely at interfaces. In cases where chemical attachmentsbetween layers are different chemical species than those within thelayers themselves it is possible to detect these attachments withsensitive bulk analyses such as solid-state nuclear magnetic resonancespectroscopy or by using other bulk analytical methods.

In the embodiments, the SOF may be a single layer (mono-segment thick ormulti-segment thick) or multiple layers (each layer being mono-segmentthick or multi-segment thick). “Thickness” refers, for example, to thesmallest dimension of the film. As discussed above, in a SOF, segmentsare molecular units that are covalently bonded through linkers togenerate the molecular framework of the film. The thickness of the filmmay also be defined in terms of the number of segments that is countedalong that axis of the film when viewing the cross-section of the film.A “monolayer” SOF is the simplest case and refers, for example, to wherea film is one segment thick. A SOF where two or more segments existalong this axis is referred to as a “multi-segment” thick SOF.

An exemplary method for preparing physically attached multilayer SOFsincludes: (1) forming a base SOF layer that may be cured by a firstcuring cycle, and (2) forming upon the base layer a second reactive wetlayer followed by a second curing cycle and, if desired, repeating thesecond step to form a third layer, a forth layer and so on. Thephysically stacked multilayer SOFs may have thicknesses greater thanabout 20 Angstroms such as, for example, the following illustrativethicknesses: about 20 Angstroms to about 10 cm, such as about 1 nm toabout 10 mm, or about 0.1 mm Angstroms to about 5 mm. In principle thereis no limit with this process to the number of layers that may bephysically stacked.

In embodiments, a multilayer SOF is formed by a method for preparingchemically attached multilayer SOFs by: (1) forming a base SOF layerhaving functional groups present on the surface (or dangling functionalgroups) from a first reactive wet layer, and (2) forming upon the baselayer a second SOF layer from a second reactive wet layer that comprisesmolecular building blocks with functional groups capable of reactingwith the dangling functional groups on the surface of the base SOFlayer. In further embodiments, a capped SOF may serve as the base layerin which the functional groups present that were not suitable orcomplementary to participate in the specific chemical reaction to linktogether segments during the base layer SOF forming process may beavailable for reacting with the molecular building blocks of the secondlayer to from an chemically bonded multilayer SOF. If desired, theformulation used to form the second SOF layer should comprise molecularbuilding blocks with functional groups capable of reacting with thefunctional groups from the base layer as well as additional functionalgroups that will allow for a third layer to be chemically attached tothe second layer. The chemically stacked multilayer SOFs may havethicknesses greater than about 20 Angstroms such as, for example, thefollowing illustrative thicknesses: about 20 Angstroms to about 10 cm,such as about 1 nm to about 10 mm, or about 0.1 mm Angstroms to about 5mm. In principle there is no limit with this process to the number oflayers that may be chemically stacked.

In embodiments, the method for preparing chemically attached multilayerSOFs comprises promoting chemical attachment of a second SOF onto anexisting SOF (base layer) by using a small excess of one molecularbuilding block (when more than one molecular building block is present)during the process used to form the SOF (base layer) whereby thefunctional groups present on this molecular building block will bepresent on the base layer surface. The surface of base layer may betreated with an agent to enhance the reactivity of the functional groupsor to create an increased number of functional groups.

In an embodiment the dangling functional groups or chemical moietiespresent on the surface of an SOF or capped SOF may be altered toincrease the propensity for covalent attachment (or, alternatively, todisfavor covalent attachment) of particular classes of molecules orindividual molecules, such as SOFs, to a base layer or any additionalsubstrate or SOF layer. For example, the surface of a base layer, suchas an SOF layer, which may contain reactive dangling functional groups,may be rendered pacified through surface treatment with a cappingchemical group. For example, a SOF layer having dangling hydroxylalcohol groups may be pacified by treatment with trimethylsiylchloridethereby capping hydroxyl groups as stable trimethylsilylethers.Alternatively, the surface of base layer may be treated with anon-chemically bonding agent, such as a wax, to block reaction withdangling functional groups from subsequent layers.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

In embodiments, a Type 1 SOF contains segments, which are not located atthe edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks. In embodiments, Type 2 and 3 SOF contains at least one segmenttype, which are not located at the edges of the SOF, that are connectedby linkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Practice of Linking Chemistry

In embodiments linking chemistry may occur wherein the reaction betweenfunctional groups produces a volatile byproduct that may be largelyevaporated or expunged from the SOF during or after the film formingprocess or wherein no byproduct is formed. Linking chemistry may beselected to achieve a SOF for applications where the presence of linkingchemistry byproducts is not desired. Linking chemistry reactions mayinclude, for example, condensation, addition/elimination, and additionreactions, such as, for example, those that produce esters, imines,ethers, carbonates, urethanes, amides, acetals, and silyl ethers.

In embodiments the linking chemistry via a reaction between functiongroups producing a non-volatile byproduct that largely remainsincorporated within the SOF after the film forming process. Linkingchemistry in embodiments may be selected to achieve a SOF forapplications where the presence of linking chemistry byproducts does notimpact the properties or for applications where the presence of linkingchemistry byproducts may alter the properties of a SOF (such as, forexample, the electroactive, hydrophobic or hydrophilic nature of theSOF). Linking chemistry reactions may include, for example,substitution, metathesis, and metal catalyzed coupling reactions, suchas those that produce carbon-carbon bonds.

For all linking chemistry the ability to control the rate and extent ofreaction between building blocks via the chemistry between buildingblock functional groups is an important aspect of the presentdisclosure. Reasons for controlling the rate and extent of reaction mayinclude adapting the film forming process for different coating methodsand tuning the microscopic arrangement of building blocks to achieve aperiodic SOF, as defined in earlier embodiments.

Innate Properties of COFs

COFs have innate properties such as high thermal stability (typicallyhigher than 400° C. under atmospheric conditions); poor solubility inorganic solvents (chemical stability), and porosity (capable ofreversible guest uptake). In embodiments, SOFs may also possess theseinnate properties.

Added Functionality of SOFs

Added functionality denotes a property that is not inherent toconventional. COFs and may occur by the selection of molecular buildingblocks wherein the molecular compositions provide the addedfunctionality in the resultant SOF. Added functionality may arise uponassembly of molecular building blocks having an “inclined property” forthat added functionality. Added functionality may also arise uponassembly of molecular building blocks having no “inclined property” forthat added functionality but the resulting SOF has the addedfunctionality as a consequence of linking segments (S) and linkers intoa SOF. Furthermore, emergence of added functionality may arise from thecombined effect of using molecular building blocks bearing an “inclinedproperty” for that added functionality whose inclined property ismodified or enhanced upon linking together the segments and linkers intoa SOF.

An Inclined Property of a Molecular Building Block

The term “inclined property” of a molecular building block refers, forexample, to a property known to exist for certain molecular compositionsor a property that is reasonably identifiable by a person skilled in artupon inspection of the molecular composition of a segment. As usedherein, the terms “inclined property” and “added functionality” refer tothe same general property (e.g., hydrophobic, electroactive, etc.) but“inclined property” is used in the context of the molecular buildingblock and “added functionality” is used in the context of the SOF.

The hydrophobic (superhydrophobic), hydrophilic, lipophobic(superlipophobic), lipophilic, photochromic and/or electroactive(conductor, semiconductor, charge transport material) nature of an SOFare some examples of the properties that may represent an “addedfunctionality” of an SOF. These and other added functionalities mayarise from the inclined properties of the molecular building blocks ormay arise from building blocks that do not have the respective addedfunctionality that is observed in the SOF.

The term hydrophobic (superhydrophobic) refers, for example, to theproperty of repelling water, or other polar species such as methanol, italso means an inability to absorb water and/or to swell as a result.Furthermore, hydrophobic implies an inability to form strong hydrogenbonds to water or other hydrogen bonding species. Hydrophobic materialsare typically characterized by having water contact angles greater than90° and superhydrophobic materials have water contact angles greaterthan 150° as measured using a contact angle goniometer or relateddevice.

The term hydrophilic refers, for example, to the property of attracting,adsorbing, or absorbing water or other polar species, or a surface thatis easily wetted by such species. Hydrophilic materials are typicallycharacterized by having less than 20° water contact angle as measuredusing a contact angle goniometer or related device. Hydrophilicity mayalso be characterized by swelling of a material by water or other polarspecies, or a material that can diffuse or transport water, or otherpolar species, through itself. Hydrophilicity, is further characterizedby being able to form strong or numerous hydrogen bonds to water orother hydrogen bonding species.

The term lipophobic (oleophobic) refers, for example, to the property ofrepelling oil or other non-polar species such as alkanes, fats, andwaxes. Lipophobic materials are typically characterized by having oilcontact angles greater than 90° as measured using a contact anglegoniometer or related device.

The term lipophilic (oleophilic) refers, for example, to the propertyattracting oil or other non-polar species such as alkanes, fats, andwaxes or a surface that is easily wetted by such species. Lipophilicmaterials are typically characterized by having a low to nil oil contactangle as measured using, for example, a contact angle goniometer.Lipophilicity can also be characterized by swelling of a material byhexane or other non-polar liquids.

The term photochromic refers, for example, to the ability to demonstratereversible color changes when exposed to electromagnetic radiation. SOFcompositions containing photochromic molecules may be prepared anddemonstrate reversible color changes when exposed to electromagneticradiation. These SOFs may have the added functionality of photochromism.The robustness of photochromic SOFs may enable their use in manyapplications, such as photochromic SOFs for erasable paper, and lightresponsive films for window tinting/shading and eye wear. SOFcompositions may contain any suitable photochromic molecule, such as adifunctional photochromic molecules as SOF molecular building blocks(chemically bound into SOF structure), a monofunctional photochromicmolecules as SOF capping units (chemically bound into SOF structure, orunfunctionalized photochromic molecules in an SOF composite (notchemically bound into SOF structure). Photochromic SOFs may change colorupon exposure to selected wavelengths of light and the color change maybe reversible.

SOF compositions containing photochromic molecules that chemically bondto the SOF structure are exceptionally chemically and mechanicallyrobust photochromic materials. Such photochromic SOF materialsdemonstrate many superior properties, such as high number of reversiblecolor change processes, to available polymeric alternatives.

The term electroactive refers, for example, to the property to transportelectrical charge (electrons and/or holes). Electroactive materialsinclude conductors, semiconductors, and charge transport materials.Conductors are defined as materials that readily transport electricalcharge in the presence of a potential difference. Semiconductors aredefined as materials do not inherently conduct charge but may becomeconductive in the presence of a potential difference and an appliedstimuli, such as, for example, an electric field, electromagneticradiation, heat, and the like. Charge transport materials are defined asmaterials that can transport charge when charge is injected from anothermaterial such as, for example, a dye, pigment, or metal in the presenceof a potential difference.

Conductors may be further defined as materials that give a signal usinga potentiometer from about 0.1 to about 10⁷ S/cm.

Semiconductors may be further defined as materials that give a signalusing a potentiometer from about 10⁻⁶ to about 10⁴ S/cm in the presenceof applied stimuli such as, for example an electric field,electromagnetic radiation, heat, and the like. Alternatively,semiconductors may be defined as materials having electron and/or holemobility measured using time-of-flight techniques in the range of 10⁻¹⁰to about 10⁶ cm² V⁻¹ s⁻¹ when exposed to applied stimuli such as, forexample an electric field, electromagnetic radiation, heat, and thelike.

Charge transport materials may be further defined as materials that haveelectron and/or hole mobility measured using time-of-flight techniquesin the range of 10⁻¹⁰ to about 10⁶ cm² V⁻¹ s⁻¹. It should be noted thatunder some circumstances charge transport materials may be alsoclassified as semiconductors.

SOFs with hydrophobic added functionality may be prepared by usingmolecular building blocks with inclined hydrophobic properties and/orhave a rough, textured, or porous surface on the sub-micron to micronscale. A paper describing materials having a rough, textured, or poroussurface on the sub-micron to micron scale being hydrophobic was authoredby Cassie and Baxter (Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc.,1944, 40, 546).

Molecular building blocks comprising or bearing highly-fluorinatedsegments have inclined hydrophobic properties and may lead to SOFs withhydrophobic added functionality. Highly-fluorinated segments are definedas the number of fluorine atoms present on the segment(s) divided by thenumber of hydrogen atoms present on the segment(s) being greater thanone. Fluorinated segments, which are not highly-fluorinated segments mayalso lead to SOFs with hydrophobic added functionality.

The above-mentioned fluorinated segments may include, for example,tetrafluorohydroquinone, perfluoroadipic acid hydrate,4,4′-(hexafluoroisopropylidene)diphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphenol, and the like.

SOFs having a rough, textured, or porous surface on the sub-micron tomicron scale may also be hydrophobic. The rough, textured, or porous SOFsurface can result from dangling functional groups present on the filmsurface or from the structure of the SOF. The type of pattern and degreeof patterning depends on the geometry of the molecular building blocksand the linking chemistry efficiency. The feature size that leads tosurface roughness or texture is from about 100 nm to about 10 μM, suchas from about 500 nm to about 5 μm.

SOFs with hydrophilic added functionality may be prepared by usingmolecular building blocks with inclined hydrophilic properties and/orcomprising polar linking groups.

Molecular building blocks comprising segments bearing polar substituentshave inclined hydrophilic properties and may lead to SOFs withhydrophilic added functionality. The term polar substituents refers, forexample, to substituents that can form hydrogen bonds with water andinclude, for example, hydroxyl, amino, ammonium, and carbonyl (such asketone, carboxylic acid, ester, amide, carbonate, urea).

SOFs with electroactive added functionality may be prepared by usingmolecular building blocks with inclined electroactive properties and/orbe electroactive resulting from the assembly of conjugated segments andlinkers. The following sections describe molecular building blocks withinclined hole transport properties, inclined electron transportproperties, and inclined semiconductor properties.

SOFs with hole transport added functionality may be obtained byselecting segment cores such as, for example, triarylamines, hydrazones(U.S. Pat. No. 7,202,002 B2 to Tokarski et al.), and enamines (U.S. Pat.No. 7,416,824 B2 to Kondoh et al.) with the following generalstructures:

The segment core comprising a triarylamine being represented by thefollowing general formula:

wherein Ar¹, Ar², Ar³, Ar⁴ and Ar⁵ each independently represents asubstituted or unsubstituted aryl group, or Ar⁵ independently representsa substituted or unsubstituted arylene group, and k represents 0 or 1,wherein at least two of Ar¹, Ar², Ar³, Ar⁴ and Ar⁵ comprises a Fg(previously defined). Ar⁵ may be further defined as, for example, asubstituted phenyl ring, substituted/unsubstituted phenylene,substituted/unsubstituted monovalently linked aromatic rings such asbiphenyl, terphenyl, and the like, or substituted/unsubstituted fusedaromatic rings such as naphthyl, anthranyl, phenanthryl, and the like.

Segment cores comprising arylamines with hole transport addedfunctionality include, for example, aryl amines such as triphenylamine,N,N,N′,N′-tetraphenyl-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-bis(4-butylphenyl)-N,N′-diphenyl-[p-terphenyl]-4,4″-diamine;hydrazones such as N-phenyl-N-methyl-3-(9-ethyl)carbazyl hydrazone and4-diethyl amino benzaldehyde-1,2-diphenyl hydrazone; and oxadiazolessuch as 2,5-bis(4-N,N′-diethylaminophenyl)-1,2,4-oxadiazole, stilbenes,and the like.

Molecular building blocks comprising triarylamine core segments withinclined hole transport properties may be derived from the list ofchemical structures including, for example, those listed below:

The segment core comprising a hydrazone being represented by thefollowing general formula:

wherein Ar¹, Ar², and Ar³ each independently represents an aryl groupoptionally containing one or more substituents, and R represents ahydrogen atom, an aryl group, or an alkyl group optionally containing asubstituent; wherein at least two of Ar¹, Ar², and Ar³ comprises a Fg(previously defined); and a related oxadiazole being represented by thefollowing general formula:

wherein Ar and Ar¹ each independently represent an aryl group thatcomprises a Fg (previously defined).

Molecular building blocks comprising hydrazone and oxadiazole coresegments with inclined hole transport properties may be derived from thelist of chemical structures including, for example, those listed below:

The segment core comprising an enamine being represented by thefollowing general formula:

wherein Ar¹, Ar², Ar³, and Ar⁴ each independently represents an arylgroup that optionally contains one or more substituents or aheterocyclic group that optionally contains one or more substituents,and R represents a hydrogen atom, an aryl group, or an alkyl groupoptionally containing a substituent; wherein at least two of Ar¹, Ar²,Ar³, and Ar⁴ comprises a Fg (previously defined).

Molecular building blocks comprising enamine core segments with inclinedhole transport properties may be derived from the list of chemicalstructures including, for example, those listed below:

SOFs with electron transport added functionality may be obtained byselecting segment cores comprising, for example, nitrofluorenones,9-fluorenylidene malonitriles, diphenoquinones, andnaphthalenetetracarboxylic diimides with the following generalstructures:

It should be noted that the carbonyl groups of diphenylquinones couldalso act as Fgs in the SOF forming process.

SOFs with semiconductor added functionality may be obtained by selectingsegment cores such as, for example, acenes,thiophenes/oligothiophenes/fused thiophenes, perylene bisimides, ortetrathiofulvalenes, and derivatives thereof with the following generalstructures:

The SOF may be a p-type semiconductor, n-type semiconductor or ambipolarsemiconductor. The SOF semiconductor type depends on the nature of themolecular building blocks. Molecular building blocks that possess anelectron donating property such as alkyl, alkoxy, aryl, and aminogroups, when present in the SOF, may render the SOF a p-typesemiconductor. Alternatively, molecular building blocks that areelectron withdrawing such as cyano, nitro, fluoro, fluorinated alkyl,and fluorinated aryl groups may render the SOF into the n-typesemiconductor.

Molecular building blocks comprising acerae core segments with inclinedsemiconductor properties may be derived from the list of chemicalstructures including, for example, those listed below:

Molecular building blocks comprising thiophene/oligothiophene/fusedthiophene core segments with inclined semiconductor properties may bederived from the list of chemical structures including, for example,those listed below:

Examples of molecular building blocks comprising perylene bisimide coresegments with inclined semiconductor properties may be derived from thechemical structure below:

Molecular building blocks comprising tetrathiofulvalene core segmentswith inclined semiconductor properties may be derived from the list ofchemical structures including, for example, those listed below:

wherein Ar each independently represents an aryl group that optionallycontains one or more substituents or a heterocyclic group thatoptionally contains one or more substituents.

Similarly, the electroactivity of SOFs prepared by these molecularbuilding blocks will depend on the nature of the segments, nature of thelinkers, and how the segments are orientated within the SOF. Linkersthat favor preferred orientations of the segment moieties in the SOF areexpected to lead to higher electroactivity.

Process for Preparing an Ordered Structured Organic Film

The process for making ordered SOFs typically comprises a number ofactivities or steps (set forth below) that may be performed in anysuitable sequence or where two or more activities are performedsimultaneously or in close proximity in time:

A process for preparing a ordered (periodic) structured organic filmcomprising:(a) preparing a liquid-containing reaction mixture comprising aplurality of molecular building blocks each comprising a segment and anumber of functional groups;(b) depositing the reaction mixture as a wet film;(c) promoting a change of the wet film including the molecular buildingblocks to a dry film comprising the SOF comprising a plurality of thesegments and a plurality of linkers arranged as a covalent organicframework, wherein at a macroscopic level the covalent organic frameworkis a film;(d) optionally removing the SOF from the coating substrate to obtain afree-standing SOF;(e) optionally processing the free-standing SOF into a roll;(f) optionally cutting and seaming the SOF into a belt; and(g) optionally performing the above SOF formation process(es) upon anSOF (which was prepared by the above SOF formation process(es)) as asubstrate for subsequent SOF formation process(es).

The above activities or steps may be conducted at atmospheric, superatmospheric, or subatmospheric pressure. The term “atmospheric pressure”as used herein refers to a pressure of about 760 torr. The term “superatmospheric” refers to pressures greater than atmospheric pressure, butless than 20 atm. The term “subatmospheric pressure” refers to pressuresless than atmospheric pressure. In an embodiment, the activities orsteps may be conducted at or near atmospheric pressure. Generally,pressures of from about 0.1 atm to about 2 atm, such as from about 0.5atm to about 1.5 atm, or 0.8 atm to about 1.2 atm may be convenientlyemployed.

Process Action A: Preparation of the Liquid-Containing Reaction Mixture

The reaction mixture comprises a plurality of molecular building blocksthat are dissolved, suspended, or mixed in a liquid. The plurality ofmolecular building blocks may be of one type or two or more types. Whenone or more of the molecular building blocks is a liquid, the use of anadditional liquid is optional. Catalysts may optionally be added to thereaction mixture to enable SOF formation or modify the kinetics of SOFformation during Action C described above. Additives or secondarycomponents may optionally be added to the reaction mixture to alter thephysical properties of the resulting SOF.

The reaction mixture components (molecular building blocks, optionally aliquid, optionally catalysts, and optionally additives) are combined ina vessel. The order of addition of the reaction mixture components mayvary; however, typically the catalyst is added last. In particularembodiments, the molecular building blocks are heated in the liquid inthe absence of the catalyst to aid the dissolution of the molecularbuilding blocks. The reaction mixture may also be mixed, stirred,milled, or the like, to ensure even distribution of the formulationcomponents prior to depositing the reaction mixture as a wet film.

In embodiments, the reaction mixture may be heated prior to beingdeposited as a wet film. This may aid the dissolution of one or more ofthe molecular building blocks and/or increase the viscosity of thereaction mixture by the partial reaction of the reaction mixture priorto depositing the wet layer. This approach may be used to increase theloading of the molecular building blocks in the reaction mixture.

In particular embodiments, the reaction mixture needs to have aviscosity that will support the deposited wet layer. Reaction mixtureviscosities range from about 10 to about 50,000 cps, such as from about25 to about 25,000 cps or from about 50 to about 1000 cps.

The molecular building block loading or “loading” in the reactionmixture is defined as the total weight of the molecular building blocksand optionally the catalysts divided by the total weight of the reactionmixture. Building block loadings may range from about 3 to 100%, such asfrom about 5 to about 50%, or from about 15 to about 40%. In the casewhere a liquid molecular building block is used as the only liquidcomponent of the reaction mixture (i.e. no additional liquid is used),the building block loading would be about 100%.

In embodiments, the reaction mixture comprises a plurality of molecularbuilding blocks that are dissolved, suspended, or mixed in a liquid. Theplurality of molecular building blocks may be of one type or two or moretypes. When one or more of the molecular building blocks is a liquid,the use of an additional liquid is optional.

Catalysts may optionally be added to the reaction mixture to enablepre-SOF formation and/or modify the kinetics of SOF formation duringAction C described above. The term “pre-SOF” may refer to, for example,at least two molecular building blocks that have reacted and have amolecular weight higher than the starting molecular building block andcontain multiple functional groups capable of undergoing furtherreactions with functional groups of other building blocks or pre-SOFs toobtain a SOF, which may be a substantially defect-free or defect-freeSOF, and/or the ‘activation’ of molecular building block functionalgroups that imparts enhanced or modified reactivity for the film formingprocess. Activation may include dissociation of a functional groupmoiety, pre-association with a catalyst, association with a solventmolecule, liquid, second solvent, second liquid, secondary component, orwith any entity that modifies functional group reactivity. Inembodiments, pre-SOF formation may include the reaction betweenmolecular building blocks or the ‘activation’ of molecular buildingblock functional groups, or a combination of the two. The formation ofthe “pre-SOF” may be achieved by in a number of ways, such as heatingthe reaction mixture, exposure of the reaction mixture to UV radiation,or any other means of partially reacting the molecular building blocksand/or activating functional groups in the reaction mixture prior todeposition of the wet layer on the substrate. Additives or secondarycomponents may optionally be added to the reaction mixture to alter thephysical properties of the resulting SOF.

The reaction mixture components (molecular building blocks, optionally aliquid, optionally catalysts, and optionally additives) are combined ina vessel. The order of addition of the reaction mixture components mayvary; however, typically when a process for preparing a SOF includes apre-SOF or formation of a pre-SOF, the catalyst, when present, may beadded to the reaction mixture before depositing the reaction mixture asa wet film. In embodiments, the molecular building blocks may be reactedactinically, thermally, chemically or by any other means with or withoutthe presence of a catalyst to obtain a pre-SOF. The pre-SOF and themolecular building blocks formed in the absence of catalyst may be maybe heated in the liquid in the absence of the catalyst to aid thedissolution of the molecular building blocks and pre-SOFs. Inembodiments, the pre-SOF and the molecular building blocks formed in thepresence of catalyst may be may be heated at a temperature that does notcause significant further reaction of the molecular building blocksand/or the pre-SOFs to aid the dissolution of the molecular buildingblocks and pre-SOFs. The reaction mixture may also be mixed, stirred,milled, or the like, to ensure even distribution of the formulationcomponents prior to depositing the reaction mixture as a wet film.

In embodiments, the reaction mixture may be heated prior to beingdeposited as a wet film. This may aid the dissolution of one or more ofthe molecular building blocks and/or increase the viscosity of thereaction mixture by the partial reaction of the reaction mixture priorto depositing the wet layer to form pre-SOFs. For example, the weightpercent of molecular building blocks in the reaction mixture that areincorporated into pre-reacted molecular building blocks pre-SOFs may beless than 20%, such as about 15% to about 1%, or 10% to about 5%. Inembodiments, the molecular weight of the 95% pre-SOF molecules is lessthan 5,000 daltons, such as 2,500 daltons, or 1,000 daltons. Thepreparation of pre-SOFs may be used to increase the loading of themolecular building blocks in the reaction mixture.

In the case of pre-SOF formation via functional group activation, themolar percentage of functional groups that are activated may be lessthan 50%, such as about 30% to about 10%, or about 10% to about 5%.

In embodiments, the two methods of pre-SOF formation (pre-SOF formationby the reaction between molecular building blocks or pre-SOF formationby the ‘activation’ of molecular building block functional groups) mayoccur in combination and the molecular building blocks incorporated intopre-SOF structures may contain activated functional groups. Inembodiments, pre-SOF formation by the reaction between molecularbuilding blocks and pre-SOF formation by the ‘activation’ of molecularbuilding block functional groups may occur simultaneously.

In embodiments, the duration of pre-SOF formation lasts about 10 secondsto about 48 hours, such as about 30 seconds to about 12 hours, or about1 minute to 6 hours.

In particular embodiments, the reaction mixture needs to have aviscosity that will support the deposited wet layer. Reaction mixtureviscosities range from about 10 to about 50,000 cps, such as from about25 to about 25,000 cps or from about 50 to about 1000 cps.

The molecular building block loading or “loading” in the reactionmixture is defined as the total weight of the molecular building blocksand optionally the catalysts divided by the total weight of the reactionmixture. Building block loadings may range from about 3 to 100%, such asfrom about 5 to about 50%, or from about 15 to about 40%. In the casewhere a liquid molecular building block is used as the only liquidcomponent of the reaction mixture (i.e. no additional liquid is used),the building block loading would be about 100%.

In embodiments, the pre-SOF may be made from building blocks with one ormore of the added functionality selected from the group consisting ofhydrophobic added functionality, superhydrophobic added functionality,hydrophilic added functionality, lipophobic added functionality,superlipophobic added functionality, lipophilic added functionality,photochromic added functionality, and electroactive added functionality.In embodiments, the inclined property of the molecular building blocksis the same as the added functionality of the pre-SOF. In embodiments,the added functionality of the SOF is not an inclined property of themolecular building blocks.

Liquids used in the reaction mixture may be pure liquids, such assolvents, and/or solvent mixtures. Liquids are used to dissolve orsuspend the molecular building blocks and catalyst/modifiers in thereaction mixture. Liquid selection is generally based on balancing thesolubility/dispersion of the molecular building blocks and a particularbuilding block loading, the viscosity of the reaction mixture, and theboiling point of the liquid, which impacts the promotion of the wetlayer to the dry SOF. Suitable liquids may have boiling points fromabout 30 to about 300° C., such as from about 65° C. to about 250° C.,or from about 100° C. to about 180° C.

Liquids can include molecule classes such as alkanes (hexane, heptane,octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane,decalin); mixed alkanes (hexanes, heptanes); branched alkanes(isooctane); aromatic compounds (toluene, o-, m-, p-xylene, mesitylene,nitrobenzene, benzonitrile, butylbenzene, aniline); ethers (benzyl ethylether, butyl ether, isoamyl ether, propyl ether); cyclic ethers(tetrahydrofuran, dioxane), esters (ethyl acetate, butyl acetate, butylbutyrate, ethoxyethyl acetate, ethyl propionate, phenyl acetate, methylbenzoate); ketones (acetone, methyl ethyl ketone, methyl isobutylketone,diethyl ketone, chloroacetone, 2-heptanone), cyclic ketones(cyclopentanone, cyclohexanone), amines (1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine;pyridine); amides (dimethylformamide, N-methylpyrrolidinone,N,N-dimethylformamide); alcohols (methanol, ethanol, n-, i-propanol, n-,t-butanol, 1-methoxy-2-propanol, hexanol, cyclohexanol, 3-pentanol,benzyl alcohol); nitriles (acetonitrile, benzonitrile, butyronitrile),halogenated aromatics (chlorobenzene, dichlorobenzene,hexafluorobenzene), halogenated alkanes (dichloromethane, chloroform,dichloroethylene, tetrachloroethane); and water.

Mixed liquids comprising a first solvent, second solvent, third solvent,and so forth may also be used in the reaction mixture. Two or moreliquids may be used to aid the dissolution/dispersion of the molecularbuilding blocks; and/or increase the molecular building block loading;and/or allow a stable wet film to be deposited by aiding the wetting ofthe substrate and deposition instrument; and/or modulate the promotionof the wet layer to the dry SOF. In embodiments, the second solvent is asolvent whose boiling point or vapor-pressure curve or affinity for themolecular building blocks differs from that of the first solvent. Inembodiments, a first solvent has a boiling point higher than that of thesecond solvent. In embodiments, the second solvent has a boiling pointequal to or less than about 130° C., such as a boiling point equal to orless than about 100° C., for example in the range of from about 30° C.to about 100° C., or in the range of from about 40° C. to about 90° C.,or about 50° C. to about 80° C.

In embodiments, the first solvent, or higher boiling point solvent, hasa boiling point equal to or greater than about 65° C., such as in therange of from about 80° C. to about 300° C., or in the range of fromabout 100° C. to about 250° C., or about 100° C. to about 180° C. Thehigher boiling point solvent may include, for example, the following(the value in parentheses is the boiling point of the compound):hydrocarbon solvents such as amylbenzene (202° C.), isopropylbenzene(152° C.), 1,2-diethylbenzene (183° C.), 1,3-diethylbenzene (181° C.),1,4-diethylbenzene (184° C.), cyclohexylbenzene (239° C.), dipentene(177° C.), 2,6-dimethylnaphthalene (262° C.), p-cymene (177° C.),camphor oil (160-185° C.), solvent naphtha (110-200° C.), cis-decalin(196° C.), trans-decalin (187° C.), decane (174° C.), tetralin (207°C.), turpentine oil (153-175° C.), kerosene (200-245° C.), dodecane(216° C.), dodecylbenzene (branched), and so forth; ketone and aldehydesolvents such as acetophenone (201.7° C.), isophorone (215.3° C.),phorone (198-199° C.), methylcyclohexanone (169.0-170.5° C.), methyln-heptyl ketone (195.3° C.), and so forth; ester solvents such asdiethyl phthalate (296.1° C.), benzyl acetate (215.5° C.),γ-butyrolactone (204° C.), dibutyl oxalate (240° C.), 2-ethylhexylacetate (198.6° C.), ethyl benzoate (213.2° C.), benzyl formate (203°C.), and so forth; diethyl sulfate (208° C.), sulfolane (285° C.), andhalohydrocarbon solvents; etherified hydrocarbon solvents; alcoholsolvents; ether/acetal solvents; polyhydric alcohol solvents; carboxylicanhydride solvents; phenolic solvents; water; and silicone solvents.

The ratio of the mixed liquids may be established by one skilled in theart. The ratio of liquids a binary mixed liquid may be from about 1:1 toabout 99:1, such as from about 1:10 to about 10:1, or about 1:5 to about5:1, by volume. When n liquids are used, with n ranging from about 3 toabout 6, the amount of each liquid ranges from about 1% to about 95%such that the sum of each liquid contribution equals 100%.

In embodiments, the mixed liquid comprises at least a first and a secondsolvent with different boiling points. In further embodiments, thedifference in boiling point between the first and the second solvent maybe from about nil to about 150° C., such as from nil to about 50° C. Forexample, the boiling point of the first solvent may exceed the boilingpoint of the second solvent by about 1° C. to about 100° C., such as byabout 5° C. to about 100° C., or by about 10° C. to about 50° C. Themixed liquid may comprise at least a first and a second solvent withdifferent vapor pressures, such as combinations of high vapor pressuresolvents and/or low vapor pressure solvents. The term “high vaporpressure solvent” refers to, for example, a solvent having a vaporpressure of at least about 1 kPa, such as about 2 kPa, or about 5 kPa.The term “low vapor pressure solvent” refers to, for example, a solventhaving a vapor pressure of less than about 1 kPa, such as about 0.9 kPa,or about 0.5 kPa. In embodiments, the first solvent may be a low vaporpressure solvent such as, for example, terpineol, diethylene glycol,ethylene glycol, hexylene glycol, N-methyl-2-pyrrolidone, andtri(ethylene glycol) dimethyl ether. A high vapor pressure solventallows rapid removal of the solvent by drying and/or evaporation attemperatures below the boiling point. High vapor pressure solvents mayinclude, for example, acetone, tetrahydrofuran, toluene, xylene,ethanol, methanol, 2-butanone and water.

In embodiments where mixed liquids comprising a first solvent, secondsolvent, third solvent, and so forth are used in the reaction mixture,promoting the change of the wet film and forming the dry SOF maycomprise, for example, heating the wet film to a temperature above theboiling point of the reaction mixture to form the dry SOF film; orheating the wet film to a temperature above the boiling point of thesecond solvent (below the temperature of the boiling point of the firstsolvent) in order to remove the second solvent while substantiallyleaving the first solvent and then after substantially removing thesecond solvent, removing the first solvent by heating the resultingcomposition at a temperature either above or below the boiling point ofthe first solvent to form the dry SOF film; or heating the wet filmbelow the boiling point of the second solvent in order to remove thesecond solvent (which is a high vapor pressure solvent) whilesubstantially leaving the first solvent and, after removing the secondsolvent, removing the first solvent by heating the resulting compositionat a temperature either above or below the boiling point of the firstsolvent to form the dry SOF film.

The term “substantially removing” refers to, for example, the removal ofat least 90% of the respective solvent, such as about 95% of therespective solvent. The term “substantially leaving” refers to, forexample, the removal of no more than 2% of the respective solvent, suchas removal of no more than 1% of the respective solvent.

These mixed liquids may be used to slow or speed up the rate ofconversion of the wet layer to the SOF in order to manipulate thecharacteristics of the SOFs. For example, in condensation andaddition/elimination linking chemistries, liquids such as water, 1°, 2°,or 3° alcohols (such as methanol, ethanol, propanol, isopropanol,butanol, 1-methoxy-2-propanol, tert-butanol) may be used.

Optionally a catalyst may be present in the reaction mixture to assistthe promotion of the wet layer to the dry SOF. Selection and use of theoptional catalyst depends on the functional groups on the molecularbuilding blocks. Catalysts may be homogeneous (dissolved) orheterogeneous (undissolved or partially dissolved) and include Brönstedacids (HCl (aq), acetic acid, p-toluenesulfonic acid, amine-protectedp-toluenesulfonic acid such as pyridium p-toluenesulfonate,trifluoroacetic acid); Lewis acids (boron trifluoroetherate, aluminumtrichloride); Brönsted bases (metal hydroxides such as sodium hydroxide,lithium hydroxide, potassium hydroxide; 1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine);Lewis bases (N,N-dimethyl-4-aminopyridine); metals (Cu bronze); metalsalts (FeCl₃, AuCl₃); and metal complexes (ligated palladium complexes,ligated ruthenium catalysts). Typical catalyst loading ranges from about0.01% to about 25%, such as from about 0.1% to about 5% of the molecularbuilding block loading in the reaction mixture. The catalyst may or maynot be present in the final SOF composition.

Optionally additives or secondary components may be present in thereaction mixture and wet layer. Such additives or secondary componentsmay also be integrated into a dry SOF. Additives or secondary componentscan be homogeneous or heterogeneous in the reaction mixture and wetlayer or in a dry SOF. The terms “additive” or “secondary component,”refer, for example, to atoms or molecules that are not covalently boundin the SOF, but are randomly distributed in the composition. Additivesmay be used to alter the physical properties of the SOF such aselectrical properties (conductivity, semiconductivity, electrontransport, hole transport), surface energy (hydrophobicity,hydrophilicity), tensile strength, thermal conductivity, impactmodifiers, reinforcing fibers, antiblocking agents, lubricants,antistatic agents, coupling agents, wetting agents, antifogging agents,flame retardants, ultraviolet stabilizers, antioxidants, biocides, dyes,pigments, odorants, deodorants, nucleating agents and the like.

Process Action B: Depositing the Reaction Mixture as a Wet Film

The reaction mixture may be applied as a wet film to a variety ofsubstrates using a number of liquid deposition techniques. The thicknessof the SOF is dependant on the thickness of the wet film and themolecular building block loading in the reaction mixture. The thicknessof the wet film is dependent on the viscosity of the reaction mixtureand the method used to deposit the reaction mixture as a wet film.

Substrates include, for example, polymers, papers, metals and metalalloys, doped and undoped forms of elements from Groups III-VI of theperiodic table, metal oxides, metal chalcogenides, and previouslyprepared SOF films. Examples of polymer film substrates includepolyesters, polyolefins, polycarbonates, polystyrenes,polyvinylchloride, block and random copolymers thereof, and the like.Examples of metallic surfaces include metallized polymers, metal foils,metal plates; mixed material substrates such as metals patterned ordeposited on polymer, semiconductor, metal oxide, or glass substrates.Examples of substrates comprised of doped and undoped elements fromGroups III-VI of the periodic table include, aluminum, silicon, siliconn-doped with phosphorous, silicon p-doped with boron, tin, galliumarsenide, lead, gallium indium phosphide, and indium. Examples of metaloxides include silicon dioxide, titanium dioxide, indium tin oxide, tindioxide, selenium dioxide, and alumina. Examples of metal chalcogenidesinclude cadmium sulfide, cadmium telluride, and zinc selenide.Additionally, it is appreciated that chemically treated or mechanicallymodified forms of the above substrates remain within the scope ofsurfaces which may be coated with the reaction mixture.

In embodiments, the substrate may be composed of, for example, silicon,glass plate, plastic film or sheet. For structurally flexible devices, aplastic substrate such as polyester, polycarbonate, polyimide sheets andthe like may be used. The thickness of the substrate may be from around10 micrometers to over 10 millimeters with an exemplary thickness beingfrom about 50 to about 100 micrometers, especially for a flexibleplastic substrate, and from about 1 to about 10 millimeters for a rigidsubstrate such as glass or silicon.

The reaction mixture may be applied to the substrate using a number ofliquid deposition techniques including, for example, spin coating, bladecoating, web coating, dip coating, cup coating, rod coating, screenprinting, ink jet printing, spray coating, stamping and the like. Themethod used to deposit the wet layer depends on the nature, size, andshape of the substrate and the desired wet layer thickness. Thethickness of the wet layer can range from about 10 nm to about 5 mm,such as from about 100 nm to about 1 mm, or from about 1 μm to about 500μm.

Process Action C: Promoting the Change of Wet Film to the Dry SOF

The term “promoting” refers, for example, to any suitable technique tofacilitate a reaction of the molecular building blocks. In the casewhere a liquid needs to be removed to form the dry film, “promoting”also refers to removal of the liquid. Reaction of the molecular buildingblocks and removal of the liquid can occur sequentially or concurrently.

In embodiments, the term “promoting” may also refer, for example, to anysuitable technique to facilitate a reaction of the molecular buildingblocks and/or pre-SOFs, such as a chemical reaction of the functionalgroups of the building blocks and/or pre-SOFs. Reaction of the molecularbuilding blocks and/or pre-SOFs and removal of the liquid can occursequentially or concurrently.

In certain embodiments, the liquid is also one of the molecular buildingblocks and is incorporated into the SOF. The term “dry SOF” refers, forexample, to substantially dry films such as, for example, asubstantially dry SOF may have a liquid content less than about 5% byweight of the SOF, or a liquid content less than about 2% by weight ofthe SOF.

Promoting the wet layer to form a dry SOF may be accomplished by anysuitable technique. Promoting the wet layer to form a dry SOF typicallyinvolves thermal treatment including, for example, oven drying, infraredradiation (IR), and the like with temperatures ranging from 40 to 350°C. and from 60 to 200° C. and from 85 to 160° C. The total heating timecan range from about four seconds to about 24 hours, such as from oneminute to 120 minutes, or from three minutes to 60 minutes.

IR promotion of the wet layer to the COF film may be achieved using anIR heater module mounted over a belt transport system. Various types ofIR emitters may be used, such as carbon IR emitters or short wave IRemitters (available from Heraerus). Additional exemplary informationregarding carbon IR emitters or short wave IR emitters is summarized inthe following Table.

Number of Module Power IR lamp Peak Wavelength lamps (kW) Carbon 2.0micron 2 - twin tube 4.6 Short wave 1.2-1.4 micron 3 - twin tube 4.5

Process Action D: Optionally Removing the SOF from the Coating Substrateto Obtain a Free-Standing SOF

In embodiments, a free-standing SOF is desired. Free-standing SOFs maybe obtained when an appropriate low adhesion substrate is used tosupport the deposition of the wet layer. Appropriate substrates thathave low adhesion to the SOF may include, for example, metal foils,metalized polymer substrates, release papers and SOFs, such as SOFsprepared with a surface that has been altered to have a low adhesion ora decreased propensity for adhesion or attachment. Removal of the SOFfrom the supporting substrate may be achieved in a number of ways bysomeone skilled in the art. For example, removal of the SOF from thesubstrate may occur by starting from a corner or edge of the film andoptionally assisted by passing the substrate and SOF over a curvedsurface.

Process Action E: Optionally Processing the Free-Standing SOF into aRoll

Optionally, a free-standing SOF or a SOF supported by a flexiblesubstrate may be processed into a roll. The SOF may be processed into aroll for storage, handling, and a variety of other purposes. Thestarting curvature of the roll is selected such that the SOF is notdistorted or cracked during the rolling process.

Process Action F: Optionally Cutting and Seaming the SOF into a Shape,Such as a Belt

The method for cutting and seaming the SOF is similar to that describedin U.S. Pat. No. 5,455,136 issued on Oct. 3, 1995 (for polymer films),the disclosure of which is herein totally incorporated by reference. AnSOF belt may be fabricated from a single SOF, a multi layer SOF or anSOF sheet cut from a web. Such sheets may be rectangular in shape or anyparticular shape as desired. All sides of the SOF(s) may be of the samelength, or one pair of parallel sides may be longer than the other pairof parallel sides. The SOF(s) may be fabricated into shapes, such as abelt by overlap joining the opposite marginal end regions of the SOFsheet. A seam is typically produced in the overlapping marginal endregions at the point of joining. Joining may be affected by any suitablemeans. Typical joining techniques include, for example, welding(including ultrasonic), gluing, taping, pressure heat fusing and thelike. Methods, such as ultrasonic welding, are desirable general methodsof joining flexible sheets because of their speed, cleanliness (nosolvents) and production of a thin and narrow seam.

Process Action G: Optionally Using a SOF as a Substrate for SubsequentSOF Formation Processes

A SOF may be used as a substrate in the SOF forming process to afford amulti-layered structured organic film. The layers of a multi-layered SOFmay be chemically bound in or in physical contact. Chemically bound,multi-layered SOFs are formed when functional groups present on thesubstrate SOF surface can react with the molecular building blockspresent in the deposited wet layer used to form the second structuredorganic film layer. Multi-layered SOFs in physical contact may notchemically bound to one another.

A SOF substrate may optionally be chemically treated prior to thedeposition of the wet layer to enable or promote chemical attachment ofa second SOF layer to form a multi-layered structured organic film.

Alternatively, a SOF substrate may optionally be chemically treatedprior to the deposition of the wet layer to disable chemical attachmentof a second SOF layer (surface pacification) to form a physical contactmulti-layered SOF.

Other methods, such as lamination of two or more SOFs, may also be usedto prepare physically contacted multi-layered SOFs.

EXAMPLES

A number of examples of the process used to make SOFs are set forthherein and are illustrative of the different compositions, conditions,techniques that may be utilized. Identified within each example are thenominal actions associated with this activity. The sequence and numberof actions along with operational parameters, such as temperature, time,coating method, and the like, are not limited by the following examples.All proportions are by weight unless otherwise indicated. The term “rt”refers, for example, to temperatures ranging from about 20° C. to about25° C. Mechanical measurements were measured on a TA Instruments DMAQ800 dynamic mechanical analyzer using methods standard in the art.Differential scanning calorimetery was measured on a TA Instruments DSC2910 differential scanning calorimeter using methods standard in theart. Thermal gravimetric analysis was measured on a TA Instruments TGA2950 thermal gravimetric analyzer using methods standard in the art.FT-IR spectra was measured on a Nicolet Magna 550 spectrometer usingmethods standard in the art. Thickness measurements <1 micron weremeasured on a Dektak 6 m Surface Profiler. Surface energies weremeasured on a Fibro DAT 1100 (Sweden) contact angle instrument usingmethods standard in the art. Unless otherwise noted, the SOFs producedin the following examples were either defect-free SOFs or substantiallydefect-free SOFs.

The SOFs coated onto Mylar were delaminated by immersion in a roomtemperature water bath. After soaking for 10 minutes the SOF filmgenerally detached from Mylar substrate. This process is most efficientwith a SOF coated onto substrates known to have high surface energy(polar), such as glass, mica, salt, and the like.

Given the examples below it will be apparent, that the compositionsprepared by the methods of the present disclosure may be practiced withmany types of components and may have many different uses in accordancewith the disclosure above and as pointed out hereinafter.

Embodiment of a Patterned SOF Composition

An embodiment of the disclosure is to attain a SOF wherein themicroscopic arrangement of segments is patterned. The term “patterning”refers, for example, to the sequence in which segments are linkedtogether. A patterned SOF would therefore embody a composition wherein,for example, segment A is only connected to segment B, and conversely,segment B is only connected to segment A. Further, a system wherein onlyone segment exists, say segment A, is employed is will be patternedbecause A is intended to only react with A. In principle a patterned SOFmay be achieved using any number of segment types. The patterning ofsegments may be controlled by using molecular building blocks whosefunctional group reactivity is intended to compliment a partnermolecular building block and wherein the likelihood of a molecularbuilding block to react with itself is minimized. The aforementionedstrategy to segment patterning is non-limiting. Instances where aspecific strategy to control patterning has not been deliberatelyimplemented are also embodied herein.

A patterned film may be detected using spectroscopic techniques that arecapable of assessing the successful formation of linking groups in aSOF. Such spectroscopies include, for example, Fourier-transfer infraredspectroscopy, Raman spectroscopy, and solid-state nuclear magneticresonance spectroscopy. Upon acquiring a data by a spectroscopictechnique from a sample, the absence of signals from functional groupson building blocks and the emergence of signals from linking groupsindicate the reaction between building blocks and the concomitantpatterning and formation of an SOF.

Different degrees of patterning are also embodied. Full patterning of aSOF will be detected by the complete absence of spectroscopic signalsfrom building block functional groups. Also embodied are SOFs havinglowered degrees of patterning wherein domains of patterning exist withinthe SOF. SOFs with domains of patterning, when measuredspectroscopically, will produce signals from building block functionalgroups which remain unmodified at the periphery of a patterned domain.

It is appreciated that a very low degree of patterning is associatedwith inefficient reaction between building blocks and the inability toform a film. Therefore, successful implementation of the process of thepresent disclosure requires appreciable patterning between buildingblocks within the SOF. The degree of necessary patterning to form a SOFis variable and can depend on the chosen building blocks and desiredlinking groups. The minimum degree of patterning required is thatrequired to form a film using the process described herein, and may bequantified as formation of about 20% or more of the intended linkinggroups, such as about 40% or more of the intended linking groups orabout 50% or more of the intended linking groups; the nominal degree ofpatterning embodied by the present disclosure is formation of about 60%of the intended linking group, such as formation of about 100% of theintended linking groups. Formation of linking groups may be detectedspectroscopically as described earlier in the embodiments.

Production of a Patterned SOF

The following experiments demonstrate the development of a patternedSOF. The activity described below is non-limiting as it will be apparentthat many types of approaches may be used to generate patterning in aSOF.

EXAMPLE 1 describes the synthesis of a Type 2 SOF wherein components arecombined such that etherification linking chemistry is promoted betweentwo building blocks. The presence of an acid catalyst and a heatingaction yield a SOF with the method described in EXAMPLE 1.

Example 1 Type 2 SOF

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block benzene-1,4-dimethanol[segment=p-xylyl; Fg=hydroxyl (—OH); (0.47 g, 3.4 mmol)] and a secondbuilding blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.12 g, 1.7 mmol)], and 17.9 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.31 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Promotion of the change of the wet film to a dry SOF. Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided a SOF having a thickness rangingfrom about 3-6 microns, which may be delaminated from the substrate as asingle free-standing SOF. The color of the SOF was green. TheFourier-transform infrared spectrum of a portion of this SOF is providedin FIG. 1.

To demonstrate that the SOF prepared in EXAMPLE 1 comprises segmentsfrom the employed molecular building blocks that are patterned withinthe SOF, three control experiments were conducted. Namely, three liquidreaction mixtures were prepared using the same procedure as set forth inAction A in EXAMPLE 1; however, each of these three formulations weremodified as follows:

-   -   (Control reaction mixture 1; Example 2) the building block        benzene-1,4-dimethanol was not included.    -   (Control reaction mixture 2; Example 3) the building block        N4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine        was not included.    -   (Control reaction mixture 3; Example 4) the catalyst        p-toluenesulfonic acid was not included

The full descriptions of the SOF forming process for the above describedcontrol experiments are detailed in EXAMPLES 2-4 below.

Example 2 Control Experiment Wherein the Building Blockbenzene-1,4-dimethanol was not Included

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.12 g, 1.7 mmol)], and 17.9 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.31 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Attempted promotion of the change of the wet film to a drySOF. The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions did not provide a film. Instead, aprecipitated powder of the building block was deposited onto thesubstrate.

Example 3 Control Experiment Wherein the Building BlockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine wasnot Included

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block benzene-1,4-dimethanol[segment=p-xylyl; Fg=hydroxyl (—OH); (0.47 g, 3.4 mmol)] and 17.9 g of1-methoxy-2-propanol. The mixture was shaken and heated to 60° C. untila homogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.31 g of a 10wt % solution of p-toluenesulfonic acid in 1-methoxy-2-propanol to yieldthe liquid containing reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Attempted promotion of the change of the wet film to a drySOF. The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions did not provide a film. Instead, aprecipitated powder of the building block was deposited onto thesubstrate.

Example 4 Control Experiment Wherein the Acid Catalyst p-toluenesulfonicacid was not Included

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block benzene-1,4-dimethanol[segment=p-xylyl; Fg=hydroxyl (—OH); (0.47 g, 3.4 mmol)] and a secondbuilding blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (−OCH₃); (1.12 g, 1.7 mmol)], and 17.9 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane to yield the liquid containingreaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Attempted promotion of the change of the wet film to a drySOF. The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions did not provide a film. Instead, aprecipitated powder of the building blocks was deposited onto thesubstrate.

As described in EXAMPLES 2-4, each of the three control reactionmixtures were subjected to Action B and Action C as outlined inEXAMPLE 1. However, in all cases a SOF did not form; the building blockssimply precipitated on the substrate. It is concluded from these resultsthat building blocks cannot react with themselves under the statedprocessing conditions nor can the building blocks react in the absenceof a promoter (p-toluenesulfonic acid). Therefore, the activitydescribed in EXAMPLE 1 is one wherein building blocks(benzene-1,4-dimethanol andN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine)can only react with each other when promoted to do so. A patterned SOFresults when the segments p-xylyl andN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine connect only with eachother. The Fourier-transform infrared spectrum, compared to that of theproducts of the control experiments (FIG. 2) of the SOF shows absence offunctional groups (notably the absence of the hydroxyl band from thebenzene-1,4-dimethanol) from the starting materials and further supportsthat the connectivity between segments has proceed as described above.Also, the complete absence of the hydroxyl band in the spectrum for theSOF indicates that the patterning is to a very high degree.

Described below are further Examples of defect-free SOFs and/orsubstantially defect-free SOFs prepared in accordance with the presentdisclosure. In the following examples (Action A) is the preparation ofthe liquid containing reaction mixture; (Action B) is the deposition ofreaction mixture as a wet film; and (Action C) is the promotion of thechange of the wet film to a dry SOF.

Example 5 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,3,5-trimethanol [segment=benzene-1,3,5-trimethyl; Fg=hydroxyl(—OH); (0.2 g, 1.2 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.59 g, 0.8 mmol)], and 8.95 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.16 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the reflective side of a metalized (TiZr) MYLAR™ substrate using aconstant velocity draw down coater outfitted with a bird bar having an20 mil gap. (Action C) The metalized MYLAR™ substrate supporting the wetlayer was rapidly transferred to an actively vented oven preheated to130° C. and left to heat for 40 min. These actions provided a SOF havinga thickness ranging from about 2-4 microns that could be delaminatedfrom the substrate as a single free-standing SOF. The color of the SOFwas green.

Example 6 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.21 g, 1.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.58 g, 0.87 mmol)], and 8.95 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.16 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the reflective side of a metalized (TiZr) MYLAR™ substrate using aconstant velocity draw down coater outfitted with a bird bar having a 20mil gap. (Action C) The metalized MYLAR™ substrate supporting the wetlayer was rapidly transferred to an actively vented oven preheated to130° C. and left to heat for 40 min. These actions provided a SOF havinga thickness ranging from about 4-5 microns that could be delaminatedfrom the substrate as a single free standing SOF. The color of the SOFwas green. The Fourier-transform infrared spectrum of a portion of thisSOF is provided in FIG. 3.

Example 7 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (—OH); (0.64 g, 4.6mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.54 g, 2.3 mmol)], and 7.51 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted, which was then filtered through a 0.45 micron PTFE membrane.To the filtered solution was added an acid catalyst delivered as 0.28 gof a 10 wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yieldthe liquid containing reaction mixture. (Action B) The reaction mixturewas applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 4 min. These actionsprovided a SOF having a thickness ranging from about 8-12 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was green.

Example 8 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.57 g, 4.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.61 g, 2.42 mmol)], and 7.51 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to rt, the solution was filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.22 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided a SOF having a thickness rangingfrom about 12-20 microns that could be delaminated from the substrate asa single free-standing film. The color of the SOF was green.

Example 9 Type 2 SOF

(Action A) The following were combined: the building block4,4′-(cyclohexane-1,1-diyl)diphenol[segment=4,4′-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (—OH); (0.97g, 6 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.21 g, 1.8 mmol)], and 7.51 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to rt, the solution was filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.22 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided a SOF having a thickness rangingfrom about 12-20 microns that could be delaminated from the substrate asa single free-standing film. The color of the SOF was green. TheFourier-transform infrared spectrum of SOF is provided in FIG. 4.

Example 10 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (—OH); (0.52 g, 3.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.26 g, 1.9 mmol)], and 6.3 g of 1,4-dioxane and 1.57 gof n-butyl acetate. The mixture was shaken and heated to 60° C. until ahomogenous solution resulted, which was then filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.28 g of a 10 wt solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having an 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 4 min. These actions provided a SOF having a thickness of 7-10microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was green.

Example 11 Type 2 SOF

(Action A) Same as EXAMPLE 7. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 20 min.These actions provided a uniformly coated multilayer device wherein theSOF had a thickness ranging from about 9-10 microns.

Example 12 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (—OH); (0.52 g, 3.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.26 g, 1.9 mmol)], and 6.3 g of 1,4-dioxane and 1.57 gof methyl isobutyl ketone. The mixture was shaken and heated to 60° C.until a homogenous solution resulted, which was then filtered through a0.45 micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.28 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having an 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 4 min. These actions provided a SOF having a thickness rangingfrom about 7-10 microns that could be delaminated from substrate as asingle free-standing film. The color of the SOF was green.

Example 13 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.47 g, 4.0mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.31 g, 2.0 mmol)], 6.3 g of 1,4-dioxane, and 1.57 g ofn-butyl acetate. The mixture was shaken and heated to 60° C. until ahomogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.22 g of a 10wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yield theliquid containing reaction mixture. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 40 min. These actionsprovided a SOF having a thickness ranging from about 8-12 microns thatcould be delaminated from the substrate as a single free-standing film.The color of the SOF was green.

Example 14 Type 2 SOF

(Action A) Same as EXAMPLE 10. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 20 min.These actions provided a uniformly coated multilayer device wherein theSOF had a thickness ranging from about 9-10 microns.

Example 15 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.47 g, 4.0mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.31 g, 2.0 mmol)], 6.3 g of 1,4-dioxane, and 1.57 g ofmethyl isobutyl ketone. The mixture was shaken and heated to 60° C.until a homogenous solution resulted. Upon cooling to room temperature,the solution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.22 g of a 10wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yield theliquid containing reaction mixture. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 40 min. These actionsprovided a SOF having a thickness ranging from about 8-12 microns thatcould be delaminated from the substrate as a single free-standing film.The color of the SOF was green.

Example 16 Type 2 SOF

(Action A) The following were combined: the building block4,4′-(cyclohexane-1,1-diyl)diphenol[segment=4,4′-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (—OH); (0.8g)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine, Fg=methoxyether (—OCH₃); (0.8 g, 1.5 mmol)], 1,4-dioxane, and 1.57 g of n-butylacetate. The mixture was shaken and heated to 60° C. until a homogenoussolution resulted. Upon cooling to rt, the solution was filtered througha 0.45 micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.22 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided SOF having a thickness of about12 microns that could be delaminated from the substrate as a singlefree-standing film. The color of the SOF was green.

Example 17 Type 2 SOF

(Action A) Same as EXAMPLE 13. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 20 min.These actions provided a uniformly coated multilayer device wherein theSOF had a thickness ranging from about 9-10 microns.

Example 18 Type 2 SOF

(Action A) The following were combined: the building block4,4′-(cyclohexane-1,1-diyl)diphenol[segment=4,4′-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (—OH); (0.8 g,3.0 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.8 g, 1.5 mmol)], 1,4-dioxane, and 1.57 g of methylisobutyl ketone. The mixture was shaken and heated to 60° C. until ahomogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.22 g of a 10wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yield theliquid containing reaction mixture. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 40 min. These actionsprovided SOF having a thickness of about 12 microns that could bedelaminated from the substrate as a single free-standing film. The colorof the SOF was green.

Example 19 Type 2 SOF

(Action A) Same as EXAMPLE 7. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was allowed to dry at ambienttemperature in an actively vented fume hood for 5 min and was thentransferred to an actively vented oven preheated to 120° C. and left toheat for 15 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness ranging from about 9-10 microns.

Example 20 Type 2 SOF

(Action A) Same as EXAMPLE 10. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was allowed to dry at ambienttemperature in an actively vented fume hood for 5 min and was thentransferred to an actively vented oven preheated to 120° C. and left toheat for 15 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness ranging from about 9-10 microns.

Example 21 Type 2 SOF

(Action A) Same as EXAMPLE 13, (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was allowed to dry at ambienttemperature in an actively vented fume hood for 5 min and was thentransferred to an actively vented oven preheated to 120° C. and left toheat for 15 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness ranging from about 9-10 micronsand could not be delaminated.

Example 22 Type 2 SOF

(Action A) Same as EXAMPLE 7. (Action B) The reaction mixture wasapplied to a layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 10 mil gap. (Action C) The supported wet layerwas allowed to dry at ambient temperature in an actively vented fumehood for 5 min and was then transferred to an actively vented ovenpreheated to 120° C. and left to heat for 15 min. These actions provideda uniformly coated multilayer device wherein the SOF had a thicknessranging from about 9-10 microns.

Example 23 Type 2 SOF

(Action A) Same as EXAMPLE 10. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 10 mil gap. (Action C) The supported wet layerwas allowed to dry at ambient temperature in an actively vented fumehood for 5 min and was then transferred to an actively vented ovenpreheated to 120° C. and left to heat for 15 min. These actions provideda uniformly coated multilayer device wherein the SOF had a thicknessranging from about 9-10 microns.

Example 24 Type 2 SOF

(Action A) Same as EXAMPLE 13. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 10 mil gap. (Action C) The supported wet layerwas allowed to dry at ambient temperature in an actively vented fumehood for 5 min and was then transferred to an actively vented ovenpreheated to 120° C. and left to heat for 15 min. These actions provideda uniformly coated multilayer device wherein the SOF had a thicknessranging from about 9-10 microns.

Example 25 Type 1 SOF

(Action A) The following were combined: the building block (4,4′,″,4′″-(biphenyl-4,4′-diylbis(azanetriyl))tetrakis(benzene-4,1-diyl))tetramethanol[segment=(4,4′,″,4′″-(biphenyl-4,4′-diylbis(azanetriyl))tetrakis(benzene-4,1-diyl);Fg=alcohol (—OH); (1.48 g, 2.4 mmol)], and 8.3 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.15 g of a 10 wt % solution ofp-toluenesulfonic acid in 1,4-dioxane to yield the liquid containingreaction mixture. (Action B) The reaction mixture was applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 25 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer wasrapidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 40 min. These actions provided SOF having a thicknessranging from about 8-24 microns. The color of the SOF was green.

Example 26 Type 1 SOF

(Action A) The following were combined: the building4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethanol[segment=(4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethyl); Fg=alcohol(—OH); (1.48 g, 4.4 mmol)], and 8.3 g of 1,4-dioxane. The mixture wasshaken and heated to 60° C. until a homogenous solution resulted. Uponcooling to room temperature, the solution was filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.15 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 15 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided SOF having a thickness rangingfrom about 6-15 microns that could be delaminated from substrate as asingle free-standing film. The color of the SOF was green. TheFourier-transform infrared spectrum of this film is provided in FIG. 5.Two-dimensional X-ray scattering data is provided in FIG. 8. As seen inFIG. 8, no signal above the background is present, indicating theabsence of molecular order having any detectable periodicity.

Example 27 Type 2 SOF

(Action A) The following were combined: the building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.26 g, 0.40 mmol)] and a second building block3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropan-1-ol[segment=3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropyl;Fg=hydroxy (—OH); (0.34 g, 0.78 mmol)], and 1.29 mL of1-methoxy-2-propanol. The mixture was shaken and heated to 60° C. untila homogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.2 g of a 10wt % solution of p-toluenesulfonic acid in 1-methoxy-2-propanol to yieldthe liquid containing reaction mixture. (Action B) The reaction mixturewas applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 150° C. and left to heat for 40 min. These actionsprovided SOF having a thickness ranging from about 15-20 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was green.

Example 28 Type 2 SOF

(Action A) Same as EXAMPLE 24. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 5 mil gap. (Action C) The supported wet layerwas rapidly transferred to an actively vented oven preheated to 130° C.and left to heat for 40 min. These actions provided a uniformly coatedmultilayer device wherein the SOF had a thickness of about 5 microns.

Example 29 Type 2 SOF

(Action A) Same as EXAMPLE 24. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder affixed to a spin coating device rotating at 750 rpm.The liquid reaction mixture was dropped at the centre rotating substrateto deposit the wet layer. (Action C) The supported wet layer was rapidlytransferred to an actively vented oven preheated to 140° C. and left toheat for 40 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness of about 0.2 microns.

Example 30 Type 2 SOF

(Action A) The following were combined: the building blockterephthalaldehyde [segment=benzene; Fg=aldehyde (—CHO); (0.18 g, 1.3mmol)] and a second building block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (0.26 g, 0.89 mmol)], and 2.5g of tetrahydrofuran. The mixture was shaken until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.045 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-tetrahydrofuran to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the reflective side of a metalized (TiZr) MYLAR™ substrate using aconstant velocity draw down coater outfitted with a bird bar having an 5mil gap. (Action C) The metalized MYLAR™ substrate supporting the wetlayer was rapidly transferred to an actively vented oven preheated to120° C. and left to heat for 40 min. These actions provided a SOF havinga thickness of about 6 microns that could be delaminated from substrateas a single free-standing film. The color of the SOF was red-orange. TheFourier-transform infrared spectrum of this film is provided in FIG. 6.

Example 31 Type 1 SOF

(Action A) The following were combined: the building block4,4′,4″-nitrilotribenzaldehyde [segment=triphenylamine; Fg=aldehyde(—CHO); (0.16 g, 0.4 mmol)] and a second building blocktris(4-aminophenyl)amine[segment triphenylamine; Fg=amine (—NH₂); (0.14g, 0.4 mmol)], and 1.9 g of tetrahydrofuran. The mixture was stirreduntil a homogenous solution resulted. Upon cooling to room temperature,the solution was filtered through a 0.45 micron PTFE membrane. (ActionB) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having an 5 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 120° C. and left toheat for 40 min. These actions provided a SOF having a thickness ofabout 6 microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was red. The Fourier-transforminfrared spectrum of this film is provided in FIG. 7.

Example 32 Type 2 SOF

(Action A) The following were combined: the building block glyoxal[segment=single covalent bond; Fg=aldehyde (—CHO); (0.31 g, 5.8mmol—added as 40 wt % solution in water i.e. 0.77 g aqueous glyoxal)]and a second building block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (1.14 g, (3.9 mmol)], and 8.27g of tetrahydrofuran. The mixture was shaken until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized. MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 120° C. and left to heat for 40 min. These actionsprovided a SOF having a thickness ranging from about 6-12 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was red.

Example 33 Type 2 SOF

(Action A) The following were combined: the building blockterephthalaldehyde [segment=benzene; Fg=aldehyde (—CHO); (0.18 g, 1.3mmol)] and a second building block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (0.26 g, 0.89 mmol)], 2.5 g oftetrahydrofuran, and 0.4 g water. The mixture was shaken until ahomogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. (Action B)The reaction mixture was applied to the reflective side of a metalized(TiZr) MYLAR™ substrate using a constant velocity draw down coateroutfitted with a bird bar having a 5 mil gap. (Action C) The metalizedMYLAR™ substrate supporting the wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 40 min.These actions provided a SOF having a thickness ranging 6 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was red-orange.

Example 34 Type 1 SOF

(Action A) The following were combined: the building block4,4′,4″-nitrilotribenzaldehyde [segment=triphenylamine; Fg=aldehyde(—CHO); (0.16 g, 0.4 mmol)] and a second building blocktris(4-aminophenyl)amine [segment=triphenylamine; Fg=amine (—NH₂); (0.14g, 0.4 mmol)], 1.9 g of tetrahydrofuran, and 0.4 g water. The mixturewas stirred until a homogenous solution resulted. Upon cooling to roomtemperature, the solution was filtered through a 0.45 micron PTFEmembrane. (Action B) The reaction mixture was applied to the reflectiveside of a metalized (TiZr) MYLAR™ substrate using a constant velocitydraw down coater outfitted with a bird bar having an 5 mil gap. (ActionC) The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 120° C. and left toheat for 40 min. These actions provided a SOF having a thickness ofabout 6 microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was red-orange.

Example 35 Type 2 SOF

(Action A) Same as EXAMPLE 28. (Action B) The reaction mixture wasdropped from a glass pipette onto a glass slide. (Action C) The glassslide was heated to 80° C. on a heating stage yielding a deep red SOFhaving a thickness of about 200 microns which could be delaminated fromthe glass slide.

Example 36 Type 1 SOF

(Action A) The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 5.12 g]; the additives Cymel303 (55 mg) and Silclean3700 (210 mg), and the catalyst Nacure XP-357 (267 mg) and1-methoxy-2-propanol (13.27 g). The mixture was mixed on a rolling waverotator for 10 min and then heated at 55° C. for 65 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. (Action B) The reaction mixture was applied to acommercially available, 30 mm drum photoreceptor using a cup coater(Tsukiage coating) at a pull-rate of 240 mm/min. (Action C) Thephotoreceptor drum supporting the wet layer was rapidly transferred toan actively vented oven preheated to 140° C. and left to heat for 40min. These actions provided a SOF having a thickness of about 6.9microns.

Example 37 Type 1 SOF with Additives

(Action A) The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 4.65 g]; the additives Cymel303 (49 mg) and Silclean3700 (205 mg), and the catalyst Nacure XP-357 (254 mg) and1-methoxy-2-propanol (12.25 g). The mixture was mixed on a rolling waverotator for 10 min and then heated at 55° C. for 65 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. A polyethylene wax dispersion (average particle size=5.5microns, 40% solids in i-propyl alcohol, 613 mg) was added to thereaction mixture which was sonicated for 10 min and mixed on the rotatorfor 30 min. (Action B) The reaction mixture was applied to acommercially available, 30 mm drum photoreceptor using a cup coater(Tsukiage coating) at a pull-rate of 240 mm/min. (Action C) Thephotoreceptor drum supporting the wet layer was rapidly transferred toan actively vented oven preheated to 140° C. and left to heat for 40min. These actions provided a film having a thickness of 6.9 micronswith even incorporation of the wax particles in the SOF.

Example 38 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 3.36 g] and the building blockN,N′-diphenyl-N,N′-bis-(3-hydroxyphenyl)-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetraphenyl-biphenyl-4,4′-diamine; Fg=hydroxyl (—OH);5.56 g]; the additives Cymel303 (480 mg) and Silclean 3700 (383 mg), andthe catalyst Nacure XP-357 (480 mg) and 1-methoxy-2-propanol (33.24 g).The mixture was mixed on a rolling wave rotator for 10 min and thenheated at 55° C. for 65 min until a homogenous solution resulted. Themixture was placed on the rotator and cooled to room temperature. Thesolution was filtered through a 1 micron PTFE membrane. (Action B) Thereaction mixture was applied to a commercially available, 30 mm drumphotoreceptor using a cup coater (Tsukiage coating) at a pull-rate of485 mm/min. (Action C) The photoreceptor drum supporting the wet layerwas rapidly transferred to an actively vented oven preheated to 140° C.and left to heat for 40 min. These actions provided a film having athickness ranging from 6.0 to 6.2 microns.

Example 39 Type 2 SOF

(Action A) The following can be combined: the building blockdipropylcarbonate [segment=carbonyl [—C(═O)—]; Fg=propoxy (CH₃CH₂CH₂O—);4.38 g, 30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg—hydroxyl (—OH); 3.24 g, 20 mmol] and catalystsodium methoxide (38 mg) and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andheated for 40 min.

Example 40 Type 2 SOF

(Action A) The following can be combined: the building blockdipropylcarbonate [segment=carbonyl [—C(═O)—]; Fg=propoxy (CH₃CH₂CH₂O—);4.38 g, 30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg—hydroxyl (—OH); 3.24 g, 20 mmol]; phosphoricacid (2 M aq, 100 mg); and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andleft to heat for 40 min.

Example 41 Type 2 SOF

(Action A) The following can be combined: the building block1,1′-carbonyldiimidazole [segment=carbonyl [—C(—O)—]; Fg=imidazole; 4.86g, 30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg—hydroxyl (—OH); 3.24 g, 20 mmol] and catalystsodium methoxide (38 mg) and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andleft to heat for 40 min.

Example 42 Type 2 SOF

(Action A) The following can be combined: the building blockcarbonyldiimidazole [segment=carbonyl [—C(—O)—]; Fg=imidazole; 4.86 g,30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg—hydroxyl (—OH); 3.24 g, 20 mmol]; phosphoricacid (2 M aq, 100 mg); and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andleft to heat for 40 min.

Example 43 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H, 4.20 g, 20 mmol] andthe building block 1,6-hexanediol [segment=hexane; Fg—hydroxyl (—OH);3.55 g, 30 mmol]; phosphoric acid (2 M aq, 100 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 44 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H, 4.20 g, 20 mmol] andthe building block 1,6-hexanediol [segment=hexane; Fg—hydroxyl (—OH);3.55 g, 30 mmol]; N,N-dimethyl-4-aminopyridine (50 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 45 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H, 4.20 g, 20 mmol] andthe building block hexamethylenediamine [segment=hexane; Fg=amine(—NH₂); 3.49 g, 30 mmol]; phosphoric acid (2 M aq, 100 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 46 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H, 4.20 g, 20 mmol] andthe building block hexamethylenediamine [segment=hexane; Fg—amine(—NH₂); 3.49 g, 30 mmol]; N,N-dimethyl-4-aminopyridine (50 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 47 Type 2 SOF

(Action A) Preparation of liquid containing reaction mixture. Thefollowing can be combined: the building block 1,4-diisocyanatobenzene[segment=phenyl; Fg=isocyanate (—N═C═O); (0.5 g, 3.1 mmol)] and a secondbuilding block 4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethanol[segment=(4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethyl); (0.69, 2.1mmol)] 10.1 g of dimethylformamide, and 1.0 g of triethylamine. Themixture is stirred until a homogenous solution is obtained. Upon coolingto room temperature, the solution is filtered through a 0.45 micron PTFEmembrane. (Action B) The reaction mixture is to be applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 8 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 120 min.

Example 48 Type 2 SOF

(Action A) Preparation of liquid containing reaction mixture. Thefollowing can be combined: the building block 1,4-diisocyanatohexane[segment=hexyl; Fg=isocyanate (—N═C═O); (0.38 g, 3.6 mmol)] and a secondbuilding block triethanolamine [segment=triethylamine; (0.81, 5.6 mmol)]10.1 g of dimethylformamide, and 1.0 g of triethylamine. The mixture isstirred until a homogenous solution is obtained. Upon cooling to roomtemperature, the solution is filtered through a 0.45 micron PTFEmembrane. (Action B) The reaction mixture is to be applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 8 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 120 min.

Example 49 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 4.24 g] and the building blockN,N′,N′-diphenyl-N,N-bis-(3-hydroxyphenyl)-terphenyl-4,4′-diamine[segment=N,N,N′,N′-tetraphenyl-terphenyl-4,4′-diamine; Fg—hydroxyl(—OH); 5.62 g]; the additives Cymel303 (530 mg) and Silclean 3700 (420mg), and the catalyst Nacure XP-357 (530 mg) and 1-methoxy-2-propanol(41.62 g). The mixture was mixed on a rolling wave rotator for 10 minand then heated at 55° C. for 65 min until a homogenous solutionresulted. The mixture was placed on the rotator and cooled to roomtemperature. The solution was filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture was applied to a commercially available,30 mm drum photoreceptor using a cup coater (Tsukiage coating) at apull-rate of 485 mm/min. (Action C) The photoreceptor drum supportingthe wet layer was rapidly transferred to an actively vented ovenpreheated to 140° C. and left to heat for 40 min. These actions provideda SOF having a thickness of 6.2 microns.

Example 49 Type 2 SOF Attempt

(Action A) Attempted preparation of the liquid containing reactionmixture. The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 5.12 g]; the additives Cymel303 (55 mg), Silclean 3700(210 mg), and 1-methoxy-2-propanol (13.27 g). The mixture was heated to55° C. for 65 min in an attempt to fully dissolve the molecular buildingblock. However it did not fully dissolve. A catalyst Nacure XP-357 (267mg) was added and the heterogeneous mixture was further mixed on arolling wave rotator for 10 min. In this Example, the catalyst was addedafter the heating step. The solution was not filtered prior to coatingdue to the amount of undissolved molecular building block. (Action B)Deposition of reaction mixture as a wet film. The reaction mixture wasapplied to a commercially available, 30 mm drum photoreceptor using acup coater (Tsukiage coating) at a pull-rate of 240 mm/min. (Action C)Promotion of the change of the wet film to a dry film. The photoreceptordrum supporting the wet layer was rapidly transferred to an activelyvented oven preheated to 140° C. and left to heat for 40 min. Theseactions did not provide a uniform film. There were some regions where anon-uniform film formed that contained particles and other regions whereno film was formed at all.

Example 50 Type 2 SOF

(Action A) The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 5.12 g]; the additives Cymel303 (55 mg) and Silclean3700 (210 mg), and the catalyst Nacure XP-357 (267 mg) and1-methoxy-2-propanol (13.27 g). The mixture was mixed on a rolling waverotator for 10 min and then heated at 55° C. for 65 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. It was noted that the viscosity of the reaction mixtureincreased after the heating step (although the viscosity of the solutionbefore and after heating was not measured). (Action B) The reactionmixture was applied to a commercially available, 30 mm drumphotoreceptor using a cup coater (Tsukiage coating) at a pull-rate of240 mm/min. (Action C) The photoreceptor drum supporting the wet layerwas rapidly transferred to an actively vented oven preheated to 140° C.and left to heat for 40 min. These actions provided a SOF having athickness of 6.9 microns.

Example 51 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 1.84 g] and the building block3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropan-1-ol[segment=3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropyl;Fg=hydroxy (—OH); (2.41 g] and a catalyst p-toluenesulphonic acid (10 wt% solution in dowanol, 460 mg) and 1-methoxy-2-propanol (16.9g—containing 50 ppm DC510). The mixture was mixed on a rolling waverotator for 5 min and then heated at 70° C. for 30 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. (Action B) The reaction mixture was applied to aproduction-coated web photoreceptor with a Hirano web coater. Syringepump speed: 4.5 mL/min. (Action C) The photoreceptor supporting the wetlayer was fed at a rate of 1.5 m/min into an actively vented ovenpreheated to 130° C. for 2 min. These actions provided a SOF overcoatlayer having a thickness of 2.1 microns on a photoreceptor.

Example 52 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg—hydroxy(—OH); 5.0 g] and the building block benzenedimethanol [segment=p-xylyl;Fg—hydroxyl (—OH); 2.32 g] and a catalyst p-toluenesulphonic acid (10 wt% solution in dowanol, 720 mg) and 1-methoxy-2-propanol (22.5g—containing 50 ppm DC510). The mixture was mixed on a rolling waverotator for 5 min and then heated at 40° C. for 5 min until a homogenoussolution resulted. The mixture was placed on the rotator and cooled toroom temperature. The solution was filtered through a 1 micron PTFEmembrane. (Action B) The reaction mixture was applied to aproduction-coated, production web photoreceptor a Hirano web coater.Syringe pump speed: 5 mL/min. (Action C) The photoreceptor supportingthe wet layer was fed at a rate of 1.5 mL/min into an actively ventedoven preheated to 130° C. for 2 min. These actions provided a SOFovercoat layer having a thickness of 2.2 microns on a photoreceptor.

Example 53 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 5.0 g] and the building block benzenedimethanol [segment=p-xylyl;Fg—hydroxyl (—OH); 2.32 g] and a catalyst p-toluenesulphonic acid (10 wt% solution in dowanol, 720 mg) and 1-methoxy-2-propanol (22.5g—containing 50 ppm DC510). The mixture was mixed on a rolling waverotator for 5 min and then heated at 40° C. for 5 min until a homogenoussolution resulted. The mixture was placed on the rotator and cooled toroom temperature. The solution was filtered through a 1 micron PTFEmembrane. (Action B) The reaction mixture was applied to aproduction-coated, production web photoreceptor with a Hirano webcoater. Syringe pump speed: 10 mL/min. (Action C) The photoreceptorsupporting the wet layer was fed at a rate of 1.5 m/min into an activelyvented oven preheated to 130° C. for 2 min. These actions provided a SOFovercoat layer having a thickness of 4.3 microns on a photoreceptor.

Example 54

(Action A) The following were combined: the building4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethanol[segment=(4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethyl); Fg=alcohol(—OH); (1.48 g, 4.4 mmol)], 0.5 g water and 7.8 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.15 g of a 10 wt % solution ofp-toluenesulfonic acid in 1,4-dioxane to yield the liquid containingreaction mixture. (Action B) The reaction mixture was applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 15 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer wasrapidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 40 min. These actions provided SOF having a thicknessranging from about 4-10 microns that could be delaminated from substrateas a single free-standing film. The color of the SOF was green.Two-dimensional X-ray scattering data is provided in FIG. 8. As seen inFIG. 8, 2θ is about 17.8 and d is about 4.97 angstroms, indicating thatthe SOF possesses molecular order having a periodicity of about 0.5 nm.

Example 55 Type 2 SOF

(Action A) The following can be combined: the building block4-hydroxybenzyl alcohol [segment=toluene; Fg=hydroxyl (—OH); (0.0272 g,0.22 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH3); (0.0728 g, 0.11 mmol)], and 0.88 g of1-methoxy-2-propanol and 0.01 g of a 10 wt % solution of silclean in1-methoxy-2-propanol. The mixture is shaken and heated to 55° C. until ahomogenous solution is obtained. Upon cooling to rt, the solution isfiltered through a 0.45 micron PTFE membrane. To the filtered solutionis added an acid catalyst delivered as 0.01 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the aluminum substrate using a constant velocity draw down coateroutfitted with a bird bar having a 5 mil gap. (Action C) The aluminumsubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 140° C. and left to heat for 40 min.

Example 56 Type 2 SOF

(Action A) The following can be combined: the building block4-(hydroxymethyl)benzoic acid [segment=4-methylbenzaldehyde; Fg=hydroxyl(—OH); (0.0314 g, 0.206 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.0686 g, 0.103 mmol)], and 0.88 g of1-methoxy-2-propanol and 0.01 g of a 10 wt % solution of silclean in1-methoxy-2-propanol. The mixture is shaken and heated to 55° C. until ahomogenous solution is obtained. Upon cooling to rt, the solution isfiltered through a 0.45 micron PTFE membrane. To the filtered solutionis added an acid catalyst delivered as 0.01 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the aluminum substrate using a constant velocity draw down coateroutfitted with a bird bar having a 5 mil gap. (Action C) The aluminumsubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 140° C. and left to heat for 40 min.

Example 57 Type 2 SOF

(Action A) The following were combined: the building block 1,4diaminobenzene [segment=benzene; Fg=amine (—NH₂); (0.14 g, 1.3 mmol)]and a second building block 1,3,5-triformylbenzene [segment=benzene;Fg=aldehyde (—CHO); (0.144 g, 0.89 mmol)], and 2.8 g of NMP. The mixturewas shaken until a homogenous solution resulted. Upon cooling to roomtemperature, the solution was filtered through a 0.45 micron PTFEmembrane. To the filtered solution was added an acid catalyst deliveredas 0.02 g of a 2.5 wt % solution of p-toluenesulfonic acid in NMP toyield the liquid containing reaction mixture. (Action B) The reactionmixture was applied quartz plate affixed to the rotating unit of avariable velocity spin coater rotating at 1000 RPM for 30 seconds.(Action C) The quartz plate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 180° C. and left toheat for 120 min. These actions provide a yellow film having a thicknessof 400 nm that can be delaminated from substrate upon immersion inwater.

It will be appreciated that several of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Variouspresently unforeseen or unanticipated alternatives, modifications,variations or improvements therein may be subsequently made by thoseskilled in the art which are also intended to be encompassed by thefollowing claims. Unless specifically recited in a claim, steps orcomponents of claims should not be implied or imported from thespecification or any other claims as to any particular order, number,position, size, shape, angle, color, or material.

1. A structured organic film (SOF) comprising a plurality of segmentsincluding at least a first segment type and a plurality of linkersincluding at least a first linker type arranged as a covalent organicframework (COF), wherein the first segment type and/or the first linkertype comprises at least one atom that is not carbon and at least aportion of the SOF is periodic.
 2. The SOF of claim 1, wherein fromabout 50% by weight to about 99% by weight of the SOF is periodic. 3.The SOF of claim 1, wherein the portion of the SOF that is periodic isuniformly distributed in the SOF.
 4. The SOF of claim 1, wherein theportion of the SOF that is periodic is not uniformly distributed in theSOF.
 5. The SOF of claim 4, wherein the SOF has an upper surface and alower surface, and from about 1% to about 5% by weight the portion ofthe SOF that is periodic is positioned closer to one of the surfaces ofthe SOF.
 6. The SOF of claim 1, wherein the edges of the SOF measurefrom about 500 nm to about 5 mm.
 7. The SOF of claim 6, wherein the SOFis one to about 50 segments thick.
 8. The SOF of claim 4, wherein theedges of the SOF measure from about 500 nm to about 5 mm.
 9. The SOF ofclaim 1, wherein the plurality of segments comprise4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethylene.
 10. The SOF of claim1, wherein the plurality of segments consists of segments having thefirst segment type comprising at least one atom that is not carbon, andthe plurality of linkers consists of linkers of the first linker type.11. The SOF of claim 1, wherein the plurality of segments comprises atleast the first segment type comprising at least one atom that is notcarbon and a second segment type that is structurally different from thefirst segment type.
 12. The SOF of claim 1, wherein the plurality oflinkers comprises at least the first linker type comprising at least oneatom that is not carbon and a second linker type that is structurallydifferent from the first linker type.
 13. The SOF of claim 1, whereinthe segments have a core selected from the group consisting of carbon,nitrogen, silicon, or phosphorous atomic cores, alkoxy cores, arylcores, carbonate cores, carbocyclic cores, carbobicyclic cores,carbotricyclic cores, and oligothiophene cores.
 14. The SOF of claim 1,wherein the linkers are selected from the group consisting of singleatom linkers, single covalent bond linkers, and double covalent bondlinkers, ester linkers, ketone linkers, amide linkers, amine linkers,imine linkers, ether linkers, urethane linkers, and carbonates linkers.15. (canceled)
 16. The SOF of claim 1, wherein the SOF has less than 10pinholes, pores or gaps greater than about 250 nanometers in diameterper cm².
 17. The SOF of claim 1, wherein the SOF is a defect-free SOF.18. The SOF of claim 1, wherein the SOF is a composite SOF.
 19. The SOFof claim 1, wherein the SOF has the added functionality ofelectroactivity.
 20. A process for preparing a structured organic film(SOF) comprising: (a) preparing a liquid-containing reaction mixturecomprising: a first solvent, a first solvent, a second solvent, and aplurality of molecular building blocks each comprising a segment andfunctional groups; (b) forming a pre-SOF; (c) depositing the reactionmixture as a wet film; and (d) promoting a change of the wet film andforming a dry SOF, wherein at least a portion of the dry SOF isperiodic.
 21. The process of claim 20, wherein the dry SOF comprises aplurality of segments including at least a first segment type, aplurality of linkers including at least a first linker type arranged asa covalent organic framework (COF), wherein the first segment typeand/or the first linker type comprises at least one atom that is notcarbon.
 22. A structured organic film (SOF) comprising a plurality ofsegments including at least a first segment type and a plurality oflinkers including at least a first linker type arranged as a covalentorganic framework (COF), wherein the first segment type and/or the firstlinker type comprises a hydrogen and at least a portion of the SOF isperiodic.
 23. The SOF of claim 22, wherein the plurality of segmentsconsists of segments having the first segment type comprising a hydrogenatom, and the plurality of linkers consists of linkers of the firstlinker type.
 24. The SOF of claim 22, wherein the plurality of segmentscomprises at least the first segment type comprising a hydrogen atom anda second segment type that is structurally different from the firstsegment type.
 25. The SOF of claim 22, wherein the plurality of linkerscomprises at least the first linker type comprising a hydrogen and asecond linker type that is structurally different from the first linkertype.
 26. The SOF of claim 22, wherein the plurality of segments have acore selected from the group consisting of carbon, nitrogen, silicon, orphosphorous atomic cores, alkoxy cores, aryl cores, carbonate cores,carbocyclic cores, carbobicyclic cores, carbotricyclic cores, andoligothiophene cores; or the plurality of linkers are selected from thegroup consisting of single atom linkers, single covalent bond linkers,and double covalent bond linkers, ester linkers, ketone linkers, amidelinkers, amine linkers, imine linkers, ether linkers, urethane linkers,and carbonates linkers.
 27. The SOF of claim 22, wherein the pluralityof segments and/or the plurality of linkers comprises at least one atomselected from the group consisting of oxygen, nitrogen, silicon,phosphorous, selenium, fluorine, boron, and sulfur.
 28. The SOF of claim22, wherein the SOF has less than 10 pinholes, pores or gaps greaterthan about 250 nanometers in diameter per cm².
 29. The SOF of claim 22,wherein the SOF is a defect-free SOF.
 30. The SOF of claim 22, whereinthe SOF is a mono-segment thick layer with a thickness of from about 10Angstroms to about 250 Angstroms; or the SOF is a multi-segment thicklayer with a thickness of from about 20 nm to about 5 mm.
 31. The SOF ofclaim 1, wherein the SOF is a mono-segment thick layer with a thicknessof from about 10 Angstroms to about 250 Angstroms; or the SOF is amulti-segment thick layer with a thickness of from about 20 nm to about5 mm.